THREE-DIMENSIONAL PRINTING OF GRAPHENE-

BASED MATERIALS AND THE APPLICATION IN

ENERGY STORAGE
Prepared by
Muhammad Umar Amin
Bsf1803018
BS Physics
University of Education
 ABSTRACT
Graphene-based materials have been extensively investigated in the energy-related applications owing
to their unique properties, such as high conductivity and mechanical flexibility. Three-dimensional (3D)
graphene architectures could further strengthen their performance and facilitate the applications in
energy storage. To fabricate 3D graphene architectures, the rapidly developed 3D printing technology
presents a lot of advantages and has received much research attention. In this paper, we reviewed the
recent research advances of 3D printing of graphene-based materials and discussed the applications in
energy storage areas. The main 3D printing techniques applied in constructing graphene-based structures
were summarized, and the characteristics of each method were briefly introduced. The current
progresses of energy storage applications, focusing on supercapacitors and energy storage batteries, were
reviewed in detail. Moreover, the future research challenges and prospects were provided in the last part,
aiming at stimulating more significant research and industrial applications in this subject.
INTRODUCTION

GRAPHENE (First discovery in 2004 by NOVOSELOV AND GEIM,)

Graphene, as a typical two-dimensional (2D)

material, is constituted by a single layer of sp2-
bonded carbon atoms with a honeycomb crystal
structure
Currently, different construction methods have been developed to fabricated
3D graphene. Based on the synthesis principles, they can be categorized into the
template method, such as template directed chemical vapor deposition and
template-directed assembly synthesis, and the self-assembly method, such as the
reduction method, cross-linking method, and solgel method. Although these
methods are able to obtain 3D graphene structures with unique properties (ultra-
low density, ultra-high porosity, high specific surface area, good electrical and
mechanical strength), their shortcomings, such as exorbitant price, poor
efficiency, and complicated procedure, limit the application in industry.
3D PRINTING METHODS FOR GRAPHENE-BASED
MATERIALS

1.Inkjet printing method

Inkjet printing is defined as a technique to construct a structure
through thin material layers deposition from precursor inks. As a
digital, non-contact and droplet-based deposition process,
inkjet printing has the advantages of low cost, environmental
friendliness, and high throughput, leading to the applications
in lots of areas. For the inkjet printing method, the properties of
the inks such as viscosity m, surface tension s, and density r
should be well controlled to satisfy certain rules for properly
working under a fixed nozzle diameter d.
2.Direct ink writing (DIW) method

DIW is also an ink-based 3D printing process which involves a

computer-controlled translation stage to generate complex 3D
structures by extrusion of the liquid ink material. As a simple,
flexible, and costless technique, DIW is promising in many engineering
applications. During DIW, the ink is extruded from
the nozzle through compressed air, which leads to the less possibility
for the nozzle clogging than inkjet printing. Even though DIW
could fabricate an object with a minimal feature size of around
250 nm and has a large freedom in material selection , it
still faces the challenges such as structural deformations and
defects.
3. Fused deposition modeling (FDM) method

Fused deposition modeling is a widely used 3D printing technology which

employs the thermoplastic polymers to fabricate the complex 3D objects. During
the printing process, the thermoplastic filaments are melted and extruded
through a heated nozzle and deposited in the semi-solid form onto a solid
substrate the commonly used thermoplastics such as polycarbonate (PC),
acrylonitrile butadiene styrene co-polymers (ABS), and polylactic acid (PLA)
usually have a low melting point. Because the products fabricated by pure
polymers generally lack mechanical strength and functionality, which would
restrict the industrial level applications, a lot of methods have been proposed to
mix the polymers with other materials such as nanoparticles, short fibers, or
continuous fibers to synthesize the composite materials which could present
improved mechanical, electrical, and thermal properties.
Stereolithography (SLA) method
SLA is the first employed 3D printing technique which evolves photosensitive resin
polymerization in a layer-by-layer manner by ultraviolet (UV) light. In 1986, charles
hull [95] invented the first 3D printer based on SLA and founded the 3D systems;
thereafter polymers became popular in the 3D printing area. SLA has the
advantages of a relatively high resolution of 0.02 mm, free of nozzle clogging,
and the ability to produce multiple products in one printing cycle. While the
requirement of photocurable materials greatly restricts the scalable
development of SLA. Besides, during the SLA process, a supported substrate is
generally needed to eliminate the plastic deformation. Currently, a lot of efforts
has been spent on the developing cheap and well-behaved liquid resin
Application of 3D-printed graphene-based material in
energy storage
Graphene-based materials have received much attention in the
Energy storage application because of the outstanding electrical
Conductivity, large mechanical strength, specific surface area, and
High chemical stability. Three-dimensional graphene architectures
could further avoid the disadvantages of aggregation and
Overlaying of graphene materials . The 3D graphene synthesized by
3D printing methods could achieve higher mass Loading and other
tailored properties, which greatly facilitate the Applications in energy
storage devices such as supercapacitors and Batteries.
Supercapacitor
Supercapacitors, which store energy through charge separation
at the electrochemical interface between electrodes and
electrolyte, have been recognized as important energy storage
devices because of their merits such as high-power density, low cost,
and long life for charging and discharging. The performance of the
supercapacitors highly depends on the properties of electrode and
electrolyte materials. Three-dimensional graphene-based structures
synthesized through 3D printing are promising and widely
demonstrated
In 2014, teressa et employed a high-pressure homogenization
method to prepare the binder-free go-based inks and used the
micro-extrusion method to print functionalized graphene-based
electrodes with high charge/discharge capability, which present
great potential in fabricating electrochemical capacitors with high
specific capacitance, large power, and energy density. By using the
same printing method (i.E. Micro-extrusion), sun et al.Fabricated
planar micro-supercapacitors based on laminated graphene films.
The as-synthesized supercapacitors exhibited high capacitive
performance, excellent cycling stability, and flexibility.
Energy storage batteries
Batteries, as devices converting stored chemical energy into
electrical energy, play an important role in energy storage because
of their high powder density and capacity. In 2013, Lewis et al. first
reported their representative work about the 3D-printed batteries
by an extrusion-based printer [135]. Then, lots of researchers focus
on using 3D printing method to synthesize batteries with high
performance. Graphene-based materials are promising in battery
applications because of their excellent properties
Conclusions and prospects
We have discussed the recent advances on the adoption of 3D printing methods
on the manufacturing 3D graphene-based architectures and the applications in
energy storage areas. Four main 3D printing techniques, i.E. Inkjet printing, direct
ink writing, fused deposition modeling, and stereolithography, are sequentially
reviewed. In addition, two types of energy storage-related applications,
supercapacitors and energy storage batteries, are summarized. From this review,
it can be derived that significant progress has been made in 3D printing of
graphene-based materials in the last few years because of the combined
multiple advantages of 3D printing process and graphene materials, which could
generate 3D complex structures with fascinating mechanical properties,
electrical, and thermal properties, enabling great potential in the applications of
energy storage devices. However, some challenges still exist among the material
preparation, printing technologies, and device design.
In conclusion, the combination of 3D printing technologies with
graphene-based materials are extremely promising, while the
applications in energy storage devices are just at the beginning.
After resolving the challenges, a large impact on energy storage
areas could be expected in the future.